1. Field of the Invention
The present invention relates to piezoelectric ceramics which can be used as materials for solid displacement elements such as ceramic actuators, and to a method for producing them, and more particularly to Pb(Ni⅓Nb⅔)O3xe2x80x94PbTiO3xe2x80x94PbZrO3 solid solution piezoelectric ceramics demonstrating far better displacement properties than piezoelectric ceramics produced by conventional manufacturing methods, as well as to a method for producing such solid solution ceramics. The piezoelectric ceramics of the present invention are useful as solid displacement elements, and can be applied to solid displacement elements such as actuators to produce solid displacement elements with displacement several times greater than that of conventional solid displacement elements, yielding the promise of lower drive voltage, greater compactness, and thus greater expansion in fields involving the application of solid displacement elements.
2. Description of the Related Art
With the advent of more compact and more intelligent electronic devices recently, the importance of ceramic actuators in the form of solid displacement elements has continued to increase. PbTiO3xe2x80x94PbZrO3 solid solutions (hereinafter referred to as PZT) comprising the perovskite compounds PbTiO3 (hereinafter referred to as PT) and PbZrO3 (hereinafter referred to as PZ) are mainly used at present as ceramic actuator materials. So-called PNNxe2x80x94PTxe2x80x94PZ solid solutions, which are Pb(Ni⅓Nb⅔)O3xe2x80x94PbTiO3xe2x80x94PbZrO3 solid solutions (hereinafter sometimes referred to as PNNxe2x80x94PTxe2x80x94PZ) obtained by mixing the complex perovskite compound Pb(Ni⅓Nb⅔)O3 (hereinafter sometimes referred to as PNN) to the above solid solutions, have also been attracting more attention recently as materials for the next generation of ceramic actuators, because they can be sintered at lower temperatures than PZT solid solutions and because they show relatively high strain (xcx9c0.12%) around a composition consisting of 50 mol % PNN-35 mol % PT-15 mol % PZ.
Although the use of ceramic actuators has been studied in a variety of industrial fields recently, the displacement afforded by conventional piezoelectric ceramics has been unsatisfactory in terms of the displacement properties required in ceramic actuator applications, making the development of novel ceramic actuator materials and the further improvement of the displacement properties of conventional materials increasingly important issues. As a result of extensive research on methods for producing PNNxe2x80x94PTxe2x80x94PZ solid solutions, the inventors have perfected the present invention upon discovering piezoelectric ceramics with far better strain properties, as well as a method for producing such piezoelectric ceramics.
PNN, which is a primary component of PNNxe2x80x94PTxe2x80x94PZ solid solutions, is known to be extremely difficult to obtain in the form of a perovskite single phase in conventional methods for producing ceramics. It is also difficult to obtain high purity ceramics by conventional ceramic manufacturing methods when attempting to produce PNNxe2x80x94PTxe2x80x94PZ solution solutions with a high proportion of PNN.
However, the use of the novel method for producing piezoelectric ceramics developed by the inventors allows high purity PNNxe2x80x94PTxe2x80x94PZ solid solution piezoelectric ceramics to be readily produced, so that ceramics with far better strain properties than conventional PNNxe2x80x94PTxe2x80x94PZ piezoelectric ceramics can be developed.
An object of the present invention is to provide piezoelectric ceramic materials having far better strain properties than that of conventional piezoelectric ceramics, as well as a novel method for producing such piezoelectric ceramics. The present invention is a solid solution piezoelectric ceramic primarily comprising the complex perovskite compound Pb(Ni⅓Nb⅔)O3, the simple perovskite compound PbTiO3, and PbZrO3, wherein the aforementioned ceramic primarily comprises compositions within a triangle in which the compositional vertices are (X=52, Y=34, Z=14), (X=49,Y=37, Z=14), and (X=49, Y=34, Z=17), where Pb(Ni⅓Nb⅔)O3 is X mol %, PbTiO3 is Y mol %, and PbZrO3 is Z mol % (X+Y+Z=100) among the triangular coordinates of the phase diagram in which the vertices are Pb(Ni⅓Nb⅔) O3, PbTiO3, and PbZrO3, as well as a method for producing such a solid solution ceramic.
The present invention provides high purity piezoelectric ceramics with a high proportion of PNN. When the piezoelectric ceramics developed in the present invention are used as ceramic actuator materials, the resulting ceramic actuators show far greater displacement than conventional ceramic actuators, with the promise of far more compact ceramic actuators and lower drive voltage, making the invention extremely valuable for industrial purposes.
The present invention, which solves the aforementioned drawbacks, comprises the following technical means.
(1) A method for producing Pb(Ni⅓Nb⅔)O3xe2x80x94PbTiO3xe2x80x94PbZrO3 solid solution piezoelectric ceramics with high purity of PNN, which comprises preparing lead oxide (PbO), nickel oxide (NiO), niobium oxide (Nb2O5), titanium oxide (TiO2), and zirconium oxide (ZrO2) as starting materials by measuring out the lead oxide (PbO) in excess of that in the perovskite composition, mixing, forming the materials, heat treating the materials in air, then dissolving unreacted materials in the heat treated materirals to separate particles thereof, molding the resulting particles, and then sintering the molded product to produce a sinter.
(2) The method for producing solid solution piezoelectric ceramics with high purity of PNN according to the above (1), wherein said ceramics primarily comprising compositions within a triangle in which the compositional vertices are (X=52, Y=34, Z=14), (X=49, Y=37, Z=14), and (X=49, Y=34, Z=17), where Pb(Ni⅓Nb⅔)O3 is X mol %, PbTiO3 is Y mol %, and PbZrO3 is Z mol % (X+Y+Z=100) among the triangular coordinates in the phase diagram in which the vertices are Pb(Ni⅓Nb⅔)O3, PbTiO3, and PbZrO3.
(3) The method according to the above (1), wherein the lead oxide (PbO) is added to the starting materials in excess of that in the perovskite composition of PNNxe2x80x94PTxe2x80x94PZ, and the materials are heat treated for 1 to 2 hours in air at 950 to 1000xc2x0 C.
The present invention is described in further detail below.
The present invention for solving the aforementioned drawbacks relates to Pb(Ni⅓Nb⅔)O3xe2x80x94PbTiO3xe2x80x94PbZrO3 solid solution piezoelectric ceramics demonstrating far better displacement properties than piezoelectric ceramics produced by conventional manufacturing methods, as well as to a method for producing such solid solution ceramics. The high-performance piezoelectric ceramics produced by this method can be used to manufacture ceramic actuators demonstrating displacement several times greater than that of conventional ceramic actuators, resulting in ceramic actuators that have extremely high displacement, that are more compact, and that require a lower drive voltage.
In the method of the present invention, lead oxide (PbO), nickel oxide (NiO), niobium oxide ((Nb2O5), titanium oxide (TiO2), and zirconium oxide (ZrO2) are used as starting materials. These materials are mixed in a predetermined ratio, such as 5 PbO+0.5 NiO+0.5 Nb2O5+1.05 TiO2+0.45 ZrO2, formed into a suitable form such as a tablet or square rod on the like, and suitably heat treated for 1 to 2 hours in air 950 to 1000xc2x0 C. As preferable examples of methods for mixing the materials, wet milling or dry milling is included, as preferable examples of forming methods, mold pressing or wet pressing is included, and as preferable examples of heat treatment, heat treatment in air is included, but the examples are not limited to the above.
The heat treated materials are treated by an acidic aqueous solution such as a 1 N acetic acid aqueous solution to dissolve unreacted materials trerefrom, and the particles of the heat treated materials are separated by filtration. The resulting particles are molded by a mold presser and sintered for 1 to 3 hours at 1100 to 1300xc2x0 C. in a PbO atmosphere or in air to produce a sinter. As preferable examples of sintering means, common sintering methods, pressurized sintering methods and the like are included, but the examples are not limited to the above.
In the present invention, it is important that an excess of PbO is added to the perovskite composition of PNNxe2x80x94PTxe2x80x94PZ, as starting materials, and that the materials are heat treated at 950xc2x0 C. or higher. In this case, for example, the lead oxide (PbO) is preferably added in an excess of about 1 mol relative to 1 mol of the perovskite composition of the aforementioned solid solutions. As will be described below, the perovskite phase yield is clearly increased with materials obtained by adding an excess of PbO to the perovskite composition, thus allowing high purity PNNxe2x80x94PTxe2x80x94PZ solid solution piezoelectric ceramics to be produced.
The piezoelectric ceramics of the present invention are produced by the aforementioned method. Among ceramics primarily comprising Pb(Ni⅓Nb⅔)O3, PbTiO3, and PbZrO3, those that may suitably be used as such piezoelectric ceramics are piezoelectric ceramics primarily comprising compositions within a triangle in which the compositional vertices are (X=52, Y=34, Z=14), (X=49, Y=37, Z=14), and (X=49, Y=34, Z=17), where Pb(Ni⅓Nb⅔)O3 is X mol %, PbTiO3 is Y mol %, and PbZrO3 is Z mol % (X+Y+Z=100) among the triangular coordinates of the phase diagram in which the vertices are Pb(Ni⅓Nb⅔)O3, PbTiO3, and PbZrO3. Trace amounts of manganese oxide (MnO), strontium oxide (SrO), and the like may suitably be added in addition to the PbO, NiO, and Nb2O5 to the aforementioned piezoelectric ceramics in order to improve or stabilize their actuator properties. Within the aforementioned compositional range, the PNNxe2x80x94PTxe2x80x94PZ piezoelectric ceramics of the present invention provide strain greater than that of existing piezoelectric ceramics.
The solid solutions produced by the method of the present invention comprise cubic particles of 0.5 to 1 xcexcm that have excellent dispersion properties, which can be sintered to obtain compact sinters with a relative density of 90% or more.
Since it was extremely difficult to obtain high purity PNN perovskite phases in conventional methods for producing ceramics, it was difficult to produce high purity PNNxe2x80x94PTxe2x80x94PZ solid solution piezoelectric ceramics, but according to the manufacturing method developed by the inventors, it has been possible to produce high purity piezoelectric ceramic starting material powder. As a result, piezoelectric ceramic compositions with substantial strain properties have been discovered, and can be used for ceramic actuators. Strain of the piezoelectric ceramics can be vastly increased by means of the compositional homogeneity and the high purity achieved in the method of synthesis in the present invention.
Differences in the homogeneity of the composition of particles produced by conventional ceramic manufacturing methods and the manufacturing method of the present invention are described in detail below.
The solid phase reaction used in conventional ceramic manufacturing methods is a heterogeneous reaction, in which the synthetic reaction of the solid solutions progress from the contact point between starting material particles. Because the transfer rate of the substances in the solid phase is generally far slower than that in other reaction sites such as gas or liquid phases, it is extremely difficult to synthesize an essentially homogenous solid solution in the solid phase, so there is some degree of compositional variation in the particles thereof produced by conventional ceramic manufacturing methods. Particles thereof thus produced by the conventional ceramic manufacturing methods have a scattered compositional distribution, and since a solid solution composition is intimately related to strain properties, it is difficult to expect an exhibition of the inherent strain properties of the solid solutions.
On the other hand, in the method of the present invention, the liquid phase of lead oxide is utilized as the reaction site. This method yields highly uniform solid solution particles with little compositional variation, because the transfer rate of the substances in the liquid phase is far more rapid than that in the solid phase. As such, the development of the inherent strain properties of solid solutions can be expected of particles produced in the manufacturing method of the present invention, and the strain properties have actually been improved far more than in conventional ceramic manufacturing methods. That is, compared to particles obtained in conventional ceramic manufacturing methods, the solid solution particles produced in the present invention are believed to have higher particle homogeneity and to be qualitatively different.